Synthesis of high-TC ferromagnetic Mn-doped ZnO nanorods by thermal evaporation

This paper reports that a large amount of Mn-doped ZnO nanorods have been synthesized through thermal evaporation. The morphologies and properties are studied with x-ray diffraction, a scanning electron microscope, transmission electron microscope and Raman spectroscope. The results indicate that the manganese atoms occupy the zinc vacancies in the wurtzite lattice of ZnO without forming secondary phases. The exact manganese content has been studied by the x-ray fluorescence spectrum. Meanwhile, the magnetic moment versus temperature result proves that the as-prepared Mn-doped ZnO nanorods show ferromagnetic properties at temperatures as high as 400 K. These studies provide a good understanding of the origin of magnetic properties in diluted magnetic semiconductors.     

Synthesis and optical properties of flower-like ZnO nanorods by thermal evaporation method

Flower-like ZnO nanorods have been synthesized by heating a mixture of ZnO/graphite powders using the thermal evaporation and vapor transport on Si (1 0 0) substrates without any catalyst. The structures, morphologies and optical properties of the products were characterized in detail by using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and Raman spectroscopy. The synthesized products consisted of large quantities of flower-like ZnO nanostructures in the form of uniform nanorods. The flower-like ZnO nanorods had high purity and well crystallized wurtzite structure, whose high crystalline quality was proved by Raman spectroscopy. The as-synthesized flower-like ZnO nanorods showed a strong ultraviolet emission at 386 nm and a weak and broad yellow-green emission in visible spectrum in its room temperature photoluminescence (PL) spectrum. In addition, the growth mechanism of the flower-like ZnO nanorods was discussed based on the reaction conditions.     

Effect of growth time on Ti-doped ZnO nanorods prepared by low-temperature chemical bath deposition

Ti-doped ZnO nanorod arrays were grown onto Si substrate using chemical bath deposition (CBD) method at 93 °C. To investigate the effect of time deposition on the morphological, and structural properties, four Ti-doped ZnO samples were prepared at various deposition periods of time (2, 3.5, 5, and 6.5 h). FESEM images displayed high-quality and uniform nanorods with a mean length strongly dependent upon deposition time; i.e. it increases for prolonged growth time. Additionally, EFTEM images reveal a strong erosion on the lateral side for the sample prepared for 6.5 h as compared to 5 h. This might be attributed to the dissolution reaction of ZnO with for prolonged growth time. XRD analysis confirms the formation of a hexagonal wurtzite-type structure for all samples with a preferred growth orientation along the c-axis direction. The (100) peak intensity was enhanced and then quenched, which might be the result of an erosion on the lateral side of nanorods as seen in EFTEM. This study confirms the important role of growth time on the morphological features of Ti-doped ZnO nanorods prepared using CBD.     

Tunable surface wettability of ZnO nanorods prepared by two-step method

Zinc oxide (ZnO) nanorods were deposited on silicon substrate by two-step method. The crystal structure, surface morphology and water contact angle (WCA) were measured by X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), and water contact angle apparatus. It is demonstrated that the WCA of the as-grown ZnO nanorods varies between 136° and 43° and the contact angle reduction rate of ZnO nanorods changes rapidly with increasing growth time. The variation of contact angle in the as-grown samples and contact angle reduction rate has been attributed to the combined effects of the proportion of nonpolar planes in the outermost surface, the area fraction of vapor on the surface and the increase of surface energy of ZnO nanorods.     

Luminescence from ZnO/MgO nanoparticle structures prepared by solution techniques

The optical and structural properties of mixed ZnO/MgO particles prepared by solution techniques are investigated by the cathodoluminescence and electron microscopy techniques. The samples annealed at 400–1000 °C show well crystalline wurtzite structure of the ZnO (MgZnO) particles with the size in range of 10–100 nm. Annealing at high temperatures (>700 °C) leads to Mg diffusion in ZnO and Mg_xZn_1−xO alloy formation. The blue shifts of the near-band-edge emission as a result of the alloy band gap widening and quantum confinement effect for the small size particles are demonstrated.     

Ultraviolet emission of ZnO film prepared by electrophoretic deposition

We deposited high quality ZnO film by electrophoretic deposition (EPD) using high quality ZnO powder prepared by solid-state pyrolytic reaction. X-ray photoelectron spectroscopy (XPS) and the infrared (IR) absorption spectrum clearly indicate that the ZnO phase powder has been prepared. Transmission electron microscope (TEM) imaging and x-ray diffraction (XRD) show that the average grain size of the powder is about 20nm. XRD and selected-area electron diffraction (SAED) reveal that the ZnO film has a polycrystalline hexagonal wurtzite structure. Only a strong ultraviolet emission peak at 390nm can be observed at room temperature.     

Photoluminescence of ZnO:Sb nanobelts fabricated by thermal evaporation method

Uniform ZnO nanobelts (NBs) were synthesized by a facile thermal evaporation method. Recombination mechanism of acceptor-related emissions in Sb doped ZnO NBs was investigated by temperature-dependent photoluminescence (PL) spectra. UV near-band-edge (NBE) emissions were dominant by acceptor-bound exciton (A⁰X) at 3.358 eV and free electron-to-acceptor (FA) at 3.322 eV transitions at 81 K. Studies on A⁰X intensity showed a quenching channel, the thermal dissociations of A⁰X to a free exciton and electron hole pair with the temperature increase. The active energy of A⁰X was estimated to be 19 meV using thermal quenching formula. The acceptor ionization energy was calculated to be 190 meV using Haynes rule. These results were very similar to those of antimony or phosphorus doped ZnO films.     

Fabrication and photoluminescence of P doped ZnO nanobelts by thermal evaporation method

Uniform and flat single crystal ZnO:P nanobelts (NBs) were fabricated on Si (1 0 0) substrates by the thermal evaporation method. The growth process, free-catalyst self-assembly vapor-solid (V-S) mechanism, was described and investigated deeply in terms of thermodynamics and kinetics. Then, the photoluminescence (PL) properties of ZnO NBs were studied in a temperature range from 10 to 270 K. At 10 K the recombination of acceptor-bound exciton (A⁰X) was predominant in the PL spectrum, and was attributed to the transition of P_Zn−2V_Zn complex bound exciton. The active energy of A⁰X and acceptor binding energy were calculated to be 17.2 and 172 meV, respectively. The calculated acceptor binding energy of P doped ZnO nanostructure is in good agreement with that of P doped ZnO film.     

Performance improvement of ZnO/P3HT hybrid UV photo-detector by interfacial Au nanolayer

In this study, a hybrid ultraviolet (UV) photo detector comprising of hydrothermally grown highly oriented Zinc Oxide nanorod arrays (ZnO NRAs) and Poly(3-hexylthiophene-2,5-diyl) (P3HT) as an active layer was fabricated and characterized. These hybrid photo detectors demonstrated a high rectification ratio (∼117) and responsivity of 10.7 A/W at −2  V under incident light of wavelength 325 nm. Further to investigate the effect of surface plasmon property of metal nanoparticles on the performance of hybrid UV photo detectors, ZnO NRAs were capped with dc sputtered gold (Au) metal nanolayer (∼5 nm) at the ZnO-P3HT interface, prior to coating P3HT layer on top of it. It was found out that upon Au coating the absorption of the ZnO was enhanced partly in the ultraviolet and visible region. In consequence the rectification ratio and responsivity of the hybrid photo detector was enhanced drastically from 117 to 1167 and 10.7 to 17.7 A/W respectively. Interestingly the reduction in dark current was observed on Au coating and it was revealed that Au nanoparticles play a key role in enhancing the performance of the hybrid photo detectors.     

Fabrication and characterization of ZnO micro and nanostructures prepared by thermal evaporation

A simple method of thermal evaporation to fabricate micro and nanostructures of zinc oxide was presented. ZnO micro and nanostructures, prepared under different quantity of O₂, were characterized by techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy and analytical transmission electron Microscope. The SEM images indicated that the products prepared under the condition of sufficient O₂ were needle-like microrods and the samples synthesized under the condition of deficient O₂ were nanorods and nanowires with very high aspect ratio. The results of XRD and Raman shifts revealed that the ZnO micro and nanostructures synthesized under different quantity of O₂ were both single crystalline with the hexagonal wurtzite structure. The HRTEM images indicated that the ZnO nanowire prepared under the condition of deficient O₂ was single crystalline and grown along the direction of [0 0 1]. Photoluminescence measurement was carried out and it showed that the spectra of ZnO micro and nanostructures prepared under different quantity of O₂ exhibited similar emission features. In addition, the growth mechanism of ZnO micro and nanostructures was preliminarily discussed.     

Comparative PL study of individual ZnO nanorods,grown by APMOCVD and CBD techniques

The photoluminescence properties of individual ZnO nanorods, grown by atmospheric pressure metalorganic chemical vapor deposition (APMOCV) and chemical bath deposition (CBD) are investigated by means of temperature dependent micro-PL. It was found that the low temperature PL spectra are driven by neutral donor bound exciton emission D⁰X, peaked at 3.359 and 3.363 eV for APMOCVD and CBD ZnO nanorods, respectively. The temperature increase causes a red energy shift of the peaks and enhancement of the free excitonic emission (FX). The FX was found to dominate after 150 K for both samples. It was observed that while APMOCVD ZnO nanorods possess a constant low signal of visible deep level emission with temperature, the ZnO nanorods grown by CBD revealed the thermal activation of deep level emission (DLE) after 130 K. The resulting room temperature DLE was a wide band located at 420–550 nm. The PL properties of individual ZnO nanorods can be of importance for their forthcoming application in future optoelectronics and photonics.     

ZnO纳米棒的低温溶液法制备、光电特性研究及其在有机/无机复合电致发光中的应用

利用水热法制备了垂直于衬底的定向生长的ZnO纳米棒,利用扫描电子显微镜及光致发光的方法对其形貌及光学特性进行了表征,利用场发射性能测试装置对ZnO纳米棒的场发射性能进行了测试.结果表明:利用水热法在较低的温度(95 ℃) 下生长了具有较好形貌和结构的ZnO纳米棒,并表现出了较好的场发射特性,当电流密度为1 μA/cm²时,开启电场是2.8 V/μm,当电场为6.4 V/μm时,电流密度可以达到0.67 mA/cm²,场增强因子为3360.稳定性测试表明,在5 h内,4.5 V/μm的电场下,其波动不超过25%.将制备的ZnO纳米棒应用到有机/无机电致发光中,其中ZnO纳米棒为电子传输层,m-MTDATA(4,4',4″-tris{N,(3-methylphenyl)-N-phenylamino}-triphenylamine) 为空穴传输层,得到了ZnO的342 nm的紫外电致发光,此发光较ZnO纳米棒光致发光的紫外发射有约40 nm的蓝移. 关键词： ZnO纳米棒 场发射 水热法 有机/无机复合电致发光     

Modified thermal evaporation process using GeO2 for growing ZnO structures

In the current work, zinc oxide (ZnO) nano/microstructures are synthesized using a modified thermal-evaporation process by introducing germanium oxide (GeO₂) powder mixed with metallic Zn powder as the raw material. Without the use of any catalyst and oxygen flow in the furnace system, GeO₂ is utilized to provide an oxygen source for the growth of ZnO structure. The samples are treated by different temperatures ranging from 500 to 900 °C. Morphology, phase structure, and photoluminescence properties are investigated by scanning electron microscopy (SEM), X-ray diffractometer (XRD) and photoluminescence (PL) spectrometer. The structures and morphologies of the samples were found to vary with growth temperature. The XRD diffraction peaks show that the films grown at temperature from 600 to 800 °C consist of hexagonal wurtzite ZnO structures. Room-temperature PL measurement revealed ZnO spectra representing two bands: near-band-edge emission in the ultraviolet (UV) region and broad deep-level emission centered at about 500 nm. The strong UV emission in the PL spectra indicates that the GeO₂ supplies sufficient oxygen for formation of ZnO structures with few oxygen vacancies. The growth mechanism and the roles of GeO₂ for formation of ZnO structures are discussed in detail.     

Field emission characteristics study for ZnO/Ag and ZnO/CNTs composites produced by DC electrophoresis

A simple controllable method is reported for the coating of ZnO nanowires with Ag nanoparticles and ZnO/carbon nanotubes (CNTs) composite. It has been achieved through DC electrophoresis AgNO₃ electrolyte and CNTs in the presence of isopropanol dispersion of ZnO nanowires. In the present work, the influence of Ag nanoparticles and CNTs on the field emission properties of the composite materials is studied. The results of this research demonstrate a remarkable enhancement of field emission current of ZnO nanowires in case of CNTs mixture and Ag nanoparticles coating.     

The structure and photoluminescence properties of ZnO nanobelts prepared by a thermal evaporation process

ZnO nanobelts had been synthesized by a simple method of thermal evaporation of Zn powders. The morphology, structure and photoluminescence (PL) properties of ZnO nanobelts were studied. The nanobelts had a single-crystal hexagonal structure and grew along the (0 0 0 1) direction with several micrometers long, 50-400 nm wide and 30-100 nm thick. Photoluminescence measurement showed that the nanobelts had an intensive near-band ultraviolet emission at about 3.3 eV. The obtained experimental data suggest that the ultraviolet PL in ZnO nanobelts originates from the recombination of the acceptor-bound excitons and free extions at room temperature. The absence of the deep level emission indicated very low impurity concentration and high crystalline quality in the ZnO nanobelts. Large-area growth and high quality indicate that the prepared ZnO nanobelts have potential application in optoelectronic devices.     

ZnO/Ag/ZnO multilayer films for the application of a very low resistance transparent electrode

Transparent conductive ZnO/Ag/ZnO multilayer electrodes having much lower electrical resistance than the widely used transparent electrodes were prepared by simultaneous RF magnetron sputtering of ZnO and DC magnetron sputtering of Ag. An Ag film with different thickness was used as intermediate metallic layers. The optimum thickness of Ag thin films was determined to be 6 nm for high optical transmittance and good electrical conductivity. With about 20-25 nm thick ZnO films, the multilayer showed high optical transmittance in the visible range of the spectrum and had color neutrality. The electrical and optical properties of the multilayers were changed mainly by Ag film properties. A high quality transparent electrode, having sheet resistance as low as 3 ohm/sq and high transmittance of 90% at 580 nm, was obtained and could be reproduced by controlling the preparation parameter properly. The above property is suitable as transparent electrode for dye sensitized solar cells (DSSC).     

Electrical and deep levels characteristics of ZnO/Si heterostructure by MOCVD deposition

ZnO films have been prepared on p-type Si substrates by metal-organic chemical vapour deposition （MOCVD） at different total gas flow rates. The current versus voltage and temperature （I - V - T） characteristics, the deep-level transient spectroscopy （DLTS） and the photoluminescence （PL） spectra of the samples were measured. DLTS shows two deep-level centres of E1 （Ec-0.13±0.02eV） and E2 （Ec-0.43±0.05eV） in sample 1202a, which has a ZnO/p-Si heterostructure. A deep level at Ec-0.13±0.01 eV was also obtained from the I -T characteristics. It was considered to be the same as E1 obtained from DLTS measurement. The emission related to this deep level center was detected by PL spectra. In addition, the energy location and the relative trap density of E1 was varied when the total gas flow rate was changed.     

Pure UV photoluminescence from ZnO thin film by thermal retardation and using an amorphous SiO2 buffer layer

ZnO/SiO₂ thin films were fabricated on Si substrates by E-beam evaporation with thermal retardation. The as-prepared films were annealed for 2 h every 100 °C in the temperature range 400-800 °C under ambient air. The structural and optical properties were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL). The XRD analysis indicated that all ZnO thin films had a highly preferred orientation with the c-axis perpendicular to the substrate. From AFM images (AFM scan size is 1 μm×1 μm), the RMS roughnesses of the films were 3.82, 5.18, 3.65, 3.40 and 13.2 nm, respectively. PL measurements indicated that UV luminescence at only 374 nm was observed for all samples. The optical quality of the ZnO film was increased by thermal retardation and by using an amorphous SiO₂ buffer layer.     

Study on the electrical and optical properties of Ag/Al-doped ZnO coatings deposited by electron beam evaporation

A layer of silver was deposited onto the surface of glass substrates, coated with AZO (Al-doped ZnO), to form Ag/AZO film structures, using e-beam evaporation techniques. The electrical and optical properties of AZO, Ag and Ag/AZO film structures were studied. The deposition of Ag layer on the surface of AZO films resulted in lowering the effective electrical resistivity with a slight reduction of their optical transmittance. Ag (11 nm)/AZO (25 nm) film structure, with an accuracy of ±0.5 nm for the thickness shows a sheet resistance as low as 5.6 ± 0.5 Ω/sq and a transmittance of about 66 ± 2%. A coating consisting of AZO (25 nm)/Ag (11 nm)/AZO (25 nm) trilayer structure, exhibits a resistance of 7.7 ± 0.5 Ω/sq and a high transmittance of 85 ± 2%. The coatings have satisfactory properties of low resistance, high transmittance and highest figure of merit for application in optoelectronics devices including flat displays, thin films transistors and solar cells as transparent conductive electrodes.